Removal of single and dual ring thiophene’s from dodecane using cavitation based processes

Utilising cavitation for enhancing oxidative desulphurization has been investigated for nearly-two decades with recent investigations shifting focus from low-capacity acoustic cavitation (AC) to scalable hydrodynamic cavitation (HC). This work focuses on developing a viable means for removing thiophene’s from fuels. In the first phase of this work, use of vortex based HC devices for removal of single and dual ring thiophenes from dodecane was investigated. HC was shown to be able to remove single ring thiophene from dodecane without using any external catalyst or additives. However, in absence of catalyst or additives, it was not possible to remove dual ring thiophenes such as dibenzothiophene using HC. Therefore, in the second phase of this work, various strategies based on use of catalyst or additives to augment cavitation based process were investigated. AC based experiments were opted for shortlisting suitable catalysts and additives for intensifying cavitation based processes. The influence of using oxidant (H₂O₂) and carboxylic acid catalysts on efficacy of removal of dual ring thiophenes is presented. Several conditions were tested, and the optimal volumetric ratios of 0.95 v/v % H₂O₂ and 6.25 v/v % HCOOH was identified and utilised throughout the remainder of the study. Regeneration of extractant which accumulates oxidised sulphur species from dodecane was also investigated using AC. The additives and process conditions reported in this work are useful for enhancing desulphurization performance.     

Properties of cat-eye modulating retro-reflector and its application with piezoelectric transducer

Piezoelectric cat-eye modulating retro-reflector (MRR) is the core component of an acousto-optic retro-identification system. The influence of the optical parameters (link distance l, lens focal length f and the detector diameter r) to the cat-eye effect was analyzed theoretically and experimentally. A piezoelectric cat-eye retro-identification (PCERI) system was built, and an information transmission ratio of 2 kHz was achieved which can satisfy an access control system.     

Exo conformers of N‐(pyridin‐2‐yl)‐ and N‐(pyridin‐3‐yl)norbornene‐5,6‐dicarboximide crystals

Two isomeric pyridine‐substituted norbornenedicarboximide derivatives, namely N‐(pyridin‐2‐yl)‐exo‐norbornene‐5,6‐dicarboximide, (I), and N‐(pyridin‐3‐yl)‐exo‐norbornene‐5,6‐dicarboximide, (II), both C₁₄H₁₂N₂O₄, have been crystallized and their structures unequivocally determined by single‐crystal X‐ray diffraction. The molecules consist of norbornene moieties fused to a dicarboximide ring substituted at the N atom by either pyridin‐2‐yl or pyridin‐3‐yl in an anti configuration with respect to the double bond, thus affording exo isomers. In both compounds, the asymmetric unit consists of two independent molecules (Z′ = 2). In compound (I), the pyridine rings of the two independent molecules adopt different conformations, i.e. syn and anti, with respect to the methylene bridge. The intermolecular contacts of (I) are dominated by C—H...O interactions. In contrast, in compound (II), the pyridine rings of both molecules have an anti conformation and the two independent molecules are linked by carbonyl–carbonyl interactions, as well as by C—H...O and C—H...N contacts.     

Three 1‐phenylindolin‐2‐one derivatives displaying different molecular dipole moments and different crystallographic symmetries

Three 1‐phenylindolin‐2‐one derivatives, namely 1‐phenylindolin‐2‐one, C₁₄H₁₁NO, (I), 5‐bromo‐1‐phenylindolin‐2‐one, C₁₄H₁₀BrNO, (II), and 5‐iodo‐1‐phenylindolin‐2‐one, C₁₄H₁₀INO, (III), have been synthesized and their structures determined. Compounds (I) and (II) crystallized in the centrosymmetric space groups Pbca and P2₁/c, respectively, while compound (III) crystallized in the polar space group Aea2. Density functional theory (DFT) calculations show that the molecular dipole moment gradually decreases in the order (I) > (II) > (III). The relatively smaller dipole moment of (III) and the larger non‐electrostatic intermolecular interactions may be the main reasons for the noncentrosymmetric and polar structure of (III).     

Selectivity in micellar catalysed reactions: The role of interfacial dipole,compartmentalisation, and specific interactions with the surfactants

Micellar catalysis is playing a major role in green chemistry with ever increasing applications in the efficient and sustainable preparation of natural compounds, drugs, and more recently organic semiconductors for printed electronics. Most of the contributions in the field focus on the developments of surfactants and suitable formulative conditions capable of reproducing – and often improving – the yield of reactions commonly performed in organic solvents. The real ambition of the micellar catalysis approach goes beyond the improvement in the sustainability of existing methods and aims at mimicking not only the efficiency but also the selectivity of enzymatic catalysis. This review summarizes relevant examples of micellar catalysis enabled, efficient, and selective transformations, and discusses the different kind of processes impacting on the product distribution depending on the details of the formulative state achieved.     

Interactions of DNA with graphene and sensing applications of graphene field-effect transistor devices: A review

Graphene field-effect transistors (GFET) have emerged as powerful detection platforms enabled by the advent of chemical vapor deposition (CVD) production of the unique atomically thin 2D material on a large scale. DNA aptamers, short target-specific oligonucleotides, are excellent sensor moieties for GFETs due to their strong affinity to graphene, relatively short chain-length, selectivity, and a high degree of analyte variability. However, the interaction between DNA and graphene is not fully understood, leading to questions about the structure of surface-bound DNA, including the morphology of DNA nanostructures and the nature of the electronic response seen from analyte binding. This review critically evaluates recent insights into the nature of the DNA graphene interaction and its affect on sensor viability for DNA, small molecules, and proteins with respect to previously established sensing methods. We first discuss the sorption of DNA to graphene to introduce the interactions and forces acting in DNA based GFET devices and how these forces can potentially affect the performance of increasingly popular DNA aptamers and even future DNA nanostructures as sensor substrates. Next, we discuss the novel use of GFETs to detect DNA and the underlying electronic phenomena that are typically used as benchmarks for characterizing the analyte response of these devices. Finally, we address the use of DNA aptamers to increase the selectivity of GFET sensors for small molecules and proteins and compare them with other, state of the art, detection methods.     

Einsatz von DMS- und Piezomeßtechnik zur direkten Schubspannungsermittlung in der Kapillarrheometrie

Zusammenfassung Der Stand der Kapillarheometrie mit den Vor- und Nachteilen der einzelnen Systeme und Meßverfahren wird dargestellt. Ausgehend von diesem Stand werden zwei alternative Meßverfahren, nämlich Piezo-Einzelkraftund DMS-Meßverfahren, zur direkten Schubspannungsermittlung besprochen und eine nach diesem Prinzip konzipierte Versuchsdüse vorgestellt. Die mit dieser Düse erhaltenen Meßergebnisse zeigen im Vergleich zu konventionell, d. h. unter Anwendung des Bagley-Verfahrens, ermittelten Fließkurven im Falle der Einzelkraftmessung gute Übereinstimmung. Das Problem der Einlaufdruckkorrektur ist bei diesem Konzept von vornherein nicht vorhanden, und der ununterbrochene Fließkanal erlaubt, bei entsprechender Erweiterung auf zwei Kraftaufnehmer, einen unproblematischen Einsatz im On-line- oder sogar im In-line-Betrieb in der Polymerverarbeitung.Schlüsselwörter Rheometrie; Kapillarrheometrie; Schubspannungsermittlung; Piezokraftmessung; DMS-Anwendung; Kunststoffschmelzen; On-line-Rheometrie

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The state-of-the-art of capillary rheometry, especially the advantages and disadvantages of different systems, is presented. Two measuring methods, a piezo single-force transducer, and a strain-gauge device combined in a testing die are compared. The strain gauges are fixed at the outside of a small capillary to detect the resulting wall shear stress between inner surface of the die and polymer flow by measuring the axial strain in the wall of the die. The single force method uses an elastic section of the die which uncouples the die from the supporting structure without changing the cross-section of the flow. The uncoupled part of the die is supported by a stiff, piezo-force transducer that detects the integral effect of wall shear stress. The resulting flow curves compare well with those using the Bagley method. With the novel die no entrance pressure-loss correction is needed. In principle, it also could be used as an on-line device for polymer processing.

Vortrag, gehalten auf der Jahrestagung der Deutschen Rheologischen Gesellschaft, TH Darmstadt, 19.–21. April 1989.     

Off-axial acoustic scattering of a high-order Bessel vortex beam by a rigid sphere

In this paper, the off-axial acoustic scattering of a high-order Bessel vortex beam by a rigid immovable (fixed) sphere is investigated. It is shown here that shifting the sphere off the axis of wave propagation induces a dependence of the scattering on the azimuthal angle. Theoretical expressions for the incident and scattered field from a rigid immovable sphere are derived. The near- and far-field acoustic scattering fields are expressed using partial wave series involving the spherical harmonics, the scattering coefficients of the sphere, the half-conical angle of the wave number components of the beam, its order and the beam-shape coefficients. The scattering coefficients of the sphere and the 3D scattering directivity plots in the near- and far-field regions are evaluated using a numerical integration procedure. The calculations indicate that the scattering directivity patterns near the sphere and in the far-field are strongly dependent upon the position of the sphere facing the incident high-order Bessel vortex beam.     

Applicability of medium-size basis sets in calculations of molecular dynamic polarisabilities

Static and dynamic average polarisabilities and polarisability anisotropies of seven linear non-polar and polar molecules are calculated within the CCS, CC2, and CC3 approximations using a range of medium-sized basis sets: the polarised LPol-n (n = ds, dl, fs, fl), the aug-pc-n (n = 1, 2), the def2-SVPD, and -TZVPD basis sets. Reference values are obtained using a hierarchy of Dunning's (d-)aug-cc-pVXZ (X = D, T, Q, 5) basis sets. The results are discussed together with the available CCSD values in terms of basis set and correlation method errors, and their ratio. Detailed analysis shows that already the def2-SVPD basis set can be used in CCS polarisability calculations. When affordable, the slightly larger aug-pc-1 basis set is recommended, as it leads to significant reduction of basis set error. The def2-TZVPD, LPol-ds, and aug-pc-2 basis sets are optimal choice within the CC2 approximation, with the latter allowing to approach the CC2 basis set limit. The LPol-ds, -dl, and def2-TZVPD sets outperform the aug-cc-pVTZ set in average polarisability CCSD calculations, with the def2-TZVPD being competitive to other reduced-size sets also in determination of polarisability anisotropy. The aug-pc-2 basis is a particularly attractive choice for CCSD, giving the accuracy of aug-cc-pVQZ at a significantly reduced computational cost. The polarisability anisotropy is shown to be more computationally demanding than the average polarisability, in particular with respect to the accuracy of the correlation method and an accurate evaluation of this property requires at least the CCSD model.     

单矢量水听器估计目标方位的方法与实验

为评估基于单矢量水听器的方位估计能力,在黄海海域对矢量水听器进行实验。矢量水听器吊放于接收船尾部,采用平均声强器和复声强器方位估计方法,并提出以概率密度值最大的方位角作为目标方位估计值的具体处理准则,对恒定方向、匀速行驶的目标船方位进行估计,并求出两种方法的方位估计误差。结果表明,水听器布放深度10 m时,对正横距离为0.42 km的航速10 kn的目标船,平均声强器方法的水平方位角估计误差18°,极角估计误差为5°,可以在离目标船最远1.17 km处估计其方位;复声强法的水平方位角估计误差为13°,极角估计误差为8°,可以在离目标船最远2.35 km处估计其方位。在有接收船的噪声干扰情况下,复声强器比平均声强器方法估计的方位更准确,可以对更远处的噪声源进行方位估计。